乙醚团簇的激光电离质谱及从头计算

应用激光多光子电离质谱与超声脉冲分子束技术研究了乙醚团簇，实验中观测到乙醚的碎片离子以及强度较小的(E)H⁺，(E)^＋₂和(E)₂H⁺(E代表CH₃CH₂OCH₂CH₃)，没有发现更大尺寸的团簇离子.结合从头计算理论，在B3LYP/6-311++G(d,p 关键词： 乙醚团簇 偶极-偶极相互作用 从头计算     

The microwave spectrum of the trans conformer of ethyl acetate

The Fourier transform microwave spectrum of ethyl acetate has been measured under molecular beam conditions. The trans conformer, where all heavy atoms are located within a mirror plane, was identified after analyzing the spectrum by comparison with theoretical calculations. The barrier to internal rotation of the acetate methyl group was found to be only 99.57(11) cm⁻¹ whereas for methyl torsion in the ethyl group a barrier of 1112.3(37) cm⁻¹ was determined. A comparison between two theoretical approaches treating the internal rotation, the so-called RAM (Rho Axis Method) and CAM (Combined Axis Method), is also performed.     

Rotational spectrum of trans-trans diethyl ether in the ground and three excited vibrational states

We report the results of a comprehensive reinvestigation of the rotational spectrum of diethyl ether based on broadband millimetre-wave spectra recently recorded at The Ohio State University and in Warsaw, covering the frequency region 108-366 GHz. The data set for the ground vibrational state of trans-trans diethyl ether has been extended to over 2000 lines and improved spectroscopic constants have been determined. Rotational spectra in the first excited vibrational states of the three lowest vibrational modes of trans-trans-diethyl ether, ν₂₀, ν₃₉, and ν₁₂ have been assigned. The v₂₀ = 1 and v₃₉ = 1 states are near 100 cm⁻¹ in vibrational term value and are coupled by a strong c-axis Coriolis interaction, which gives rise to many spectacular manifestations in the rotational spectrum. All of these effects have been successfully fitted for a dataset comprising over 3000 transitions, leading to precise determination of the energy difference between these states, (ΔE/hc)=10.400222(5) cm⁻¹. A newly developed software package for assignment and analysis of broadband spectra is described and made available.     

Submillimeter-wave spectrum of anti–anti and anti–gauche diethyl ether

Measurements of the rotational spectrum of diethyl ether have been extended up to 903 GHz for the aa-conformer and up to 638 GHz for the ag-conformer. These measurements supplement previous ones up to 366 GHz and improve predictions into the THz region to be used in particular for astronomical searches for this species using the next-generation of radio-astronomy instruments such as the Atacama Large Millimeter Array.     

Millimeter-wave spectrum and ab initio DFT calculation of the C-gauche conformer of allyl isocyanate

The analysis of the ground state rotational spectrum of the C-gauche conformer of allyl isocyanate has been extended up to the frequency range of 100.0 GHz. A detailed centrifugal distortion analysis has been carried out using previously reported and newly measured transition frequencies. More accurate values of the rotational and centrifugal distortion constants are presented. Quantum chemical calculations at DFT levels of theory using large basis sets b3lyp/6-311G(d, p), have also been made to compute rotational constants, dipole moments and potential energies for different conformers of this molecule. Finally, different bond lengths and centrifugal distortion constants for the C-gauche conformer have been computed.     

乙醚团簇在纳秒激光场中的多价电离及其电子能量分布的研究

用5ns,1064nm的脉冲Nd:YAG激光,研究了乙醚团簇与纳秒激光的相互作用.在10¹¹ W/cm²量级光强下,观察到价电子完全剥离的O⁶⁺,C⁴⁺,且这些高价离子的强度比值基本不随激光能量而变化.用阻滞电压方法测量了电离过程中溢出电子能量分布,在最大激光能量4.0×10¹¹ W/cm²,溢出电子的平均能量为56eV,最大能量为102eV.实验结果支持了高价离子产生的“多 关键词： 高价离子 电子能量 纳秒激光 乙醚团簇     

Pyrolysis of ortho-cyanotoluene and PCl3 mixtures: the millimeter and submillimeter-wave spectrum of NCCCCP

The unstable NCCCCP molecule has been detected in the pyrolysis products of phosphorus trichloride and ortho-cyanotoluene mixtures. Its rotational spectrum has been investigated in the millimeter and submillimeter-wave regions for the ground and various vibrationally excited states which approximately lie below 400 cm⁻¹, namely (v₈,v₉)=(0,1),(0,2),(0,3),(0,4),(1,0), and (1,1). Transitions up to J=241←240 were measured for the ground state, making a precise evaluation of the sextic centrifugal distortion constant possible. The l-type resonances between the different sublevels of the bending states have been taken into account in the analysis of the spectra, which yielded accurate determinations of the x_L(99) and x_L(89) anharmonicity constants.     

Velocity modulation spectroscopy of molecular ions II: The millimeter/submillimeter-wave spectrum of TiF (XΦr)

The pure rotational spectrum of the molecular ion TiF⁺ in its ³Φ_r ground state has been measured in the range 327-542 GHz using millimeter-wave direct absorption techniques combined with velocity modulation spectroscopy. TiF⁺ was made in an AC discharge from a mixture of TiCl₄, F₂ in He, and argon. Ten transitions of this ion were recorded. In every transition, fluorine hyperfine interactions, as well as the fine structure splittings, were resolved. The fine structure pattern was found to be regular with almost equal spacing in frequency between the three spin components, in contrast to TiCl⁺, which is perturbed in the ground state. The data were fit with a case (a) Hamiltonian and rotational, fine structure, and hyperfine constants were determined. The bond length established for TiF⁺, r₀ = 1.7775 Å, was found to be shorter than that of TiF, r₀ = 1.8342 Å—also established from mm-wave data. The hyperfine parameters determined are consistent with a δ¹π¹ electron configuration with the electrons primarily located on the titanium nucleus. The nuclear spin-orbit constant a indicates that the unpaired electrons are closer to the fluorine nucleus in TiF⁺ relative to TiF, as expected with the decrease in bond length for the ion. The shorter bond distance is thought to arise from increased charge on the titanium nucleus as a result of a Ti²⁺F⁻ configuration. A similar decrease in bond length was found for TiCl⁺ relative to TiCl.     

The electronic spectrum of AgBr2: Ab initio benchmark vs. DFT calculations on the lowest ligand-field states including spin-orbit effects

The X²Π_g, ²Σ_g⁺ and ²Δ_g states of AgBr₂ have been studied through benchmark ab initio CASSCF + Averaged Coupled Pair Functional (ACPF) and DFT calculations using especially developed valence basis sets to study the transition energies, geometries, vibrational frequencies, Mulliken charges and spin densities. The spin-orbit (SO) effects were included through the effective hamiltonian formalism using the |ΛSΣ〉 ACPF energies as diagonal elements. At the ACPF level, the ground state is ²Π_g, in contradiction with ligand-field theory and Hartree-Fock results. The ACPF adiabatic excitation energies of the ²Σ_g⁺ and ²Δ_g states are 3825 and 20 152 cm⁻¹, respectively. The inclusion of the SO effects leads to a pure Ω = 3/2 (²Π_g) ground state, a Ω = 1/2 (97% ²Π_g + 3% ²Σ_g⁺) A state, a Ω = 1/2 (3% ²Π_g + 97% ²Σ_g⁺) B state, a Ω = 5/2 (²Δ_g) C state and a Ω = 3/2 (99% ²Δ_g) D state. The B97, B3LYP and PBE0 functionals, which were shown to yield accurate transition energies for CuCl₂, overestimate the X²Π_g-²Σ_g⁺ T_e by around 25% but provide a qualitative energetic ordering in agreement with CASSCF and ACPF results. The nature of the bonding in the X²Π_g ground state is different from that of AgCl₂ since the Mulliken charge on the metal is 0.95 while the spin density is only 0.39. DFT strongly delocalizes the spin density providing even smaller values of around 0.13 on Ag not only for the ground state, but also for the ²Σ_g⁺ state.     

Microwave spectrum, molecular structure, and theoretical calculation of cyclohexanone oxime (chair form)

The microwave spectra of cyclohexanone oxime and d₁ (=NOD) and d₄(2,2,6,6-d₄) derivatives were observed in the frequency range from 8 to 40 GHz in the ground and excited vibrational states. The rotational constants were determined to be A = 3799.844(48), B = 1513.7912(23), and C = 1189.6118(29) MHz for normal species, A = 3791.835(88), B = 1461.0324(47), and C = 1157.5653(53) MHz for d₁ species, and A = 3364.141(49), B = 1487.9551(34), and C = 1154.0965(44) MHz for d₄ species in the ground vibrational state. The planar moments, P_bb (P_bb = (I_c + I_a − I_b)/2) of normal, d₁, and d₄ species were determined to be 111.9885(26), 111.9817(46), and 124.2394(49) uŲ, respectively. The almost same values of P_bb of normal and d₁ species suggest that the hydroxyl hydrogen atom is very close to the a-c plane. From the r_s coordinates of the hydroxyl hydrogen atom, the OH bond was found to be at the trans position with respect to the CN double bond. The conformation of cyclohexanone oxime was determined to be chair form by comparing the observed and calculated rotational constants, ΔI, and planar moments, and taking account of the calculated the relative energy difference, ΔE. The structural parameters, the three bond lengths, three bond angles, and three dihedral angles, were adjusted to the nine rotational constants observed. The bond angle of ∠C₂C₁N is much wider than that of ∠C₆C₁N by about 10°. The dihedral angles of ∠C₁C₂C₃C₄, ∠C₂C₃C₄C₅, and ∠C₃C₄C₅C₆ were determined to be 53.3(5), −57.2(5), and 57.2(5)°. Two vibrational modes were assigned to the ring-bending and ring-twisting ones, which are almost harmonic up to v = 3.     

Millimeterwave rotational spectrum and internal rotation in o-chlorotoluene

The millimeterwave rotational spectrum of o-chlorotoluene is investigated in the frequency region 150-250 GHz. Many rotational lines show splitting due to internal rotation of the methyl group. The analysis of the internal rotation splitting allows us to determine with precision the potential barrier to internal rotation of the methyl group. However, it is found that the moment of inertia of the methyl top is probably much smaller than usually assumed, which significantly affects the value of the barrier. Accurate centrifugal distortion constants are obtained for the ground states of ³⁵Cl and ³⁷Cl isotopologues as well as for an excited vibrational state.     

Excess isentropic compressibility and speed of sound of the ternary mixture 2-propanol + diethyl ether + n-hexane and the constituent binary mixtures at 298.15 K

Speed of sound and densities of the ternary mixture 2-propanol + diethyl ether + n-hexane and also the binary mixtures 2-propanol + diethyl ether and 2-propanol + n-hexane have been measured at the entire composition range at 298.15 K. The excess isentropic compressibilities and the excess speed of the sound have been calculated from experimental densities and speed of sound. These excess properties of the binary mixtures were fitted to Redlich-Kister equation, while the Cibulka’s equation was used to fit the values related to the values to the ternary system. These excess properties have been used to discuss the presence of significant interactions between the component molecules in the binary mixtures and also the ternary mixtures. Speed of sound of the binary mixtures and the ternary mixture have been compared with calculated values from free length theory (FLT), collision factor theory (CFT), Nomoto’s relation (NR), Van Deal’s ideal mixing relation (IMR) and Junjie’s relation (JR). The results are used to compare the relative merits of these theories and relations in terms of the root mean square deviation relative (RMSD_r).     

Fourier-transform microwave and submillimeter-wave spectroscopy of chloroiodomethane, CH2ICl

Guided by a previous microwave study (9–35 GHz), the rotational spectrum of both chlorine isotopologues of chloroiodomethane in its vibrational and electronic ground state has been re-investigated in the microwave region and extended to the millimeter/submillimeter-wave region. Weak a-type transitions have been recorded by Fourier transform microwave spectroscopy below 20 GHz whilst strong b-type rotational transitions have been recorded between 15 and 646 GHz, corresponding to energy levels with J″ ≤ 108 and . Molecular constants including those describing the hyperfine structures owing to the two halogen atoms were accurately determined for both species from the least-squares analysis of a total of 1475 distinct transition frequencies (of which 906 belong to the CH₂I³⁵Cl isotopologue). The two sets of rotational constants allowed us to derive an r₀ structure of CH₂ICl.     

Microwave spectrum of trans 3-fluorophenol in excited torsional states

The microwave rotational spectra of the trans conformer of 3-fluorophenol have been observed in excited torsional states and analyzed in the frequency range 12.0-43.0 GHz using conventional microwave and Radio-Frequency Microwave Double Resonance (RFMWDR) techniques. Analysis of the ground torsional state spectrum has been extended to higher rotational states. Least-squares analysis of three sets of rotational transitions yield rotational and centrifugal distortion constants for the ground and first two excited torsional states. A nonlinear behavior of the variation of inertial defect with the torsional quantum number was observed.     

The submillimeter-wave spectrum of the chloromethyl radical, CH2Cl, in the ground vibronic state

We have extended the measurement of submillimeter wave transitions of CH₂Cl between 418 and 470 GHz for the two isotopic species of Cl. The radical was produced in a fast flow system by hydrogen abstraction of CH₃Cl by Cl atoms obtained from a 2450 MHz microwave discharge in Cl₂ diluted with helium. A global least-squares analysis including the previous and the newly observed transitions led to a more precise set of rotational, fine and hyperfine constants for the two isotopomers in their ground vibronic state. In addition, we have also observed CH₂Cl by the 248 nm photolysis of CH₂BrCl, leading to a single 1/e lifetime of 146 ms.     

The pure rotational spectra of the two lowest energy conformers of the asymmetric ether C4H9OC2H5

An experimental study has been performed shedding light on the conformational energies of the asymmetric ether n-butyl ethyl ether. Rotational spectroscopy between 7.8 GHz and 16.2 GHz has identified two conformers of n-butyl ethyl ether, C₄H₉OC₂H₅. In these experiments spectra were observed as the target compound participated in an argon expansion from high to low pressure causing molecular rotational temperatures to be below 4 K. For one conformer, 95 pure rotational transitions have been recorded, for the second conformer, 20 pure rotational transitions were recorded. Rotational constants and centrifugal distortion constants are presented for both butyl ethyl ether conformers. The structures of both conformers have been identified by exploring the multi-dimensional molecular potential energy surface using ab initio calculations. From the numerous low energy conformers identified using ab initio methods, the three lowest conformers were pursued at increasingly higher levels of theory, i.e. complete basis set extrapolations, coupled cluster methods, and also taking into consideration zero point vibrational energies. The two conformers observed experimentally are only revealed to be the two lowest energy conformers when high levels of quantum chemical methodologies are employed.     

Formation of vinylidene and vinylene by selective reactivity of Si(1 0 0)2 × 1 towards iso, cis and trans isomers of dichloroethylene

The room temperature (RT) chemisorption of three (iso, cis and trans) isomers of dichloroethylene (DCE) on Si(1 0 0)2 × 1 have been investigated by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). Unlike ethylene, the lack of molecular desorption features in the TPD data effectively rules out the cycloaddition adsorption mechanism for all three isomers. XPS spectra show that cis- and trans-DCE adsorb dissociatively on the 2 × 1 surface in equal proportion as mono-σ bonded 2-chlorovinyl and di-σ bonded vinylene adspecies, which could be produced by dechlorination mechanisms involving the proposed tri-atom π-complex and diradical intermediates, respectively. Acetylene (m/z 26) evolution from 2-chlorovinyl adspecies at 590 K and vinylene at 750 K are also observed for both cis- and trans-DCE, further confirming the common adsorption mechanisms for these geometrical isomers and the relative stabilities of the adspecies. In contrast, only vinylidene adspecies is found for iso-DCE, which indicates that the high ionicity of the CCl₂ group favours the diradical dechlorination mechanism. The single m/z 26 desorption peak for iso-DCE adspecies observed at a higher temperature (780 K) than cis and trans isomers is consistent with the higher adsorption energy of vinylidene than vinylene on Si(1 0 0) obtained in our ab initio calculations. The different relative locations of the Cl atoms in these isomers therefore play a crucial role in controlling the adsorption and thermal evolution on Si(1 0 0)2 × 1. The selective reactivity of the 2 × 1 surface towards these isomers can be used to generate vinylene or vinylidene templates from their corresponding adspecies.     

Fourier transform microwave spectroscopy of N,N-dimethylacetamide

The jet-cooled Fourier-transform microwave spectrum of N,N-dimethylacetamide was recorded in the region of 12-24 GHz, and was analyzed to determine rotational constants and nuclear quadrupole coupling constants. Coriolis-like coupling parameters characterizing interaction between internal rotation of methyl groups and the overall rotation were also determined from internal-rotation tunneling splittings of the rotational transitions. The Coriolis-like coupling parameters permitted determination of the barrier heights to internal rotation of the three methyl groups, which were found to be 677, 237, and 183 cm⁻¹ for the C-methyl top, the trans-N-methyl top and the cis-N-methyl top, respectively.     

The rotational spectrum of tertiary-butyl alcohol

The rotational spectrum of tertiary-butyl alcohol has been recorded in selected regions between 8 and 500 GHz. Early data from the University of Wisconsin in the 8-40 GHz region have been combined with recent measurements from the University of Bologna and the Jet Propulsion Laboratory in the millimeter and submillimeter wavelength regions. The spectrum was fit over a wide range of J’s and K’s using a common set of parameters for both the A and E states. This paper describes the initial assignment at Wisconsin and the final procedure used to assign and fit the higher rotational states. The resulting molecular constants and their interpretation are discussed.